CN112661133A - Preparation method of hard carbon material - Google Patents
Preparation method of hard carbon material Download PDFInfo
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- CN112661133A CN112661133A CN202011540987.8A CN202011540987A CN112661133A CN 112661133 A CN112661133 A CN 112661133A CN 202011540987 A CN202011540987 A CN 202011540987A CN 112661133 A CN112661133 A CN 112661133A
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- hard carbon
- carbon material
- precursor
- material according
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 64
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000007833 carbon precursor Substances 0.000 claims abstract description 16
- 239000010426 asphalt Substances 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 238000003763 carbonization Methods 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000010000 carbonizing Methods 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 14
- 239000011295 pitch Substances 0.000 claims description 11
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 9
- 244000060011 Cocos nucifera Species 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 238000005245 sintering Methods 0.000 claims description 8
- 238000010902 jet-milling Methods 0.000 claims description 7
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 239000011304 carbon pitch Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 239000002028 Biomass Substances 0.000 abstract description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000003610 charcoal Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000011534 incubation Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000009656 pre-carbonization Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method of a hard carbon material, which comprises the steps of pre-carbonizing a carbon-containing raw material with natural components to prepare a precursor; preliminarily crushing the precursor to prepare a crushed product; under the inert atmosphere, the crushed material is sintered at high temperature for carbonization to prepare a hard carbon precursor; stirring, heating and mixing the hard carbon precursor and the asphalt for coating treatment to obtain a coated product; carbonizing the coated hard carbon precursor and asphalt in vacuum, and crushing and grading to obtain a hard carbon material; the invention uses natural biomass as raw material, and coats the surface, thereby reducing production cost, improving first coulombic efficiency and first discharge capacity, and improving the performance of hard carbon material.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a preparation method of a hard carbon material.
Background
At present, a carbon-based material is a main material of a lithium battery negative electrode material, wherein a hard carbon material has the advantages of long cycle life, good power performance, low lithium ion intercalation expansion rate and the like, compared with graphite, the structure of the hard carbon material is isotropic, and the content of oxygen-containing groups on the surface of the hard carbon material is far higher than that of the graphite material, so that the first coulombic efficiency and the first discharge capacity of the conventional hard carbon material are poor, the performance potential of the hard carbon material is limited, and the application of the hard carbon material in the lithium battery material is far lower than that of the graphite negative electrode material, and therefore, the conventional hard carbon negative electrode material needs to be further improved.
Disclosure of Invention
The invention aims to provide a preparation method of a hard carbon material, aiming at the problems, the invention provides the preparation method of the hard carbon material, which utilizes natural biomass components as raw materials to coat the surfaces of the raw materials, reduces the production cost, improves the first coulombic efficiency and the first discharge capacity, and improves the performance of the hard carbon material.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
a preparation method of a hard carbon material comprises the following steps,
s1, pre-carbonizing a carbon-containing raw material with natural components to prepare a precursor;
s2, primarily crushing the precursor to prepare a crushed product;
s3, sintering the crushed material at high temperature in an inert atmosphere for carbonization to obtain a hard carbon precursor; during sintering of the particles of the comminuted material, volatile substances form gas molecules which escape and form pores in the hard carbon structure.
S4, stirring, heating and mixing the hard carbon precursor and the pitch for coating treatment to obtain a coated product;
and S5, carbonizing the coated hard carbon precursor and the asphalt in vacuum, and crushing and grading to obtain the hard carbon material.
Preferably, in the step S1, the raw material is coconut shell, and the raw material is heated under the protection of N2; optionally, the heating temperature is 400-700 ℃, and the heating time is 30-120 min.
Preferably, in the step S2, the particle size D50 of the material after the primary pulverization treatment is 5 to 50 μm; the smaller particle size can ensure more uniform sintering of the material in the carbon burning process and homogenization and refinement of the coating process.
Preferably, in S3, the inert atmosphere includes a nitrogen atmosphere, an argon atmosphere or a helium atmosphere; preferably, the sintering temperature of carbonization is 1150-1600 ℃, and the treatment time is 1-20 h; further preferably, the sintering temperature of carbonization is 1350-1425 ℃, and the treatment time is 1-20 h.
Preferably, in S4, the coated hard carbon precursor and pitch are subjected to jet milling, and preferably, the jet milling equipment adopts a jet mill; preferably, the particle size D50 of the jet milled material is 4-10 μm.
Preferably, in S4, the asphalt-coated device is a reaction kettle, so that the asphalt and the hard carbon particles are uniformly mixed; preferably, the mass ratio of the pitch to the hard carbon precursor is 1: 13.5-21.5.
Preferably, in S5, the heating temperature is 1700-2000 ℃, so that the asphalt is converted into a graphite structure; preferably, the vacuum is less than 0.01 Pa.
Preferably, in S5, the crushed hard carbon material has an average particle size of 3-25um, a small particle size, a short inter-particle distance, a fine and dense microporous structure, a large void volume, and is convenient for lithium ions to enter, so that the capacity is high, and the cycle, power and rate performance of the prepared battery is good; the tap density is 0.6-1.2g/cm3, and the specific surface area is 2.5-8.5m 2/g.
Compared with the prior art, the preparation method of the hard carbon material adopting the technical scheme has the following beneficial effects:
firstly, the preparation method of the hard carbon material adopts natural coconut shells as raw materials, the raw materials are environment-friendly and rich in source, the cost is low, the best carbonization effect is obtained through the pre-carbonization, impurity removal, primary crushing and classification of the raw materials, and the prepared hard carbon has rich amorphous microporous structures.
Secondly, performing asphalt coating on the surface of the hard carbon material to form a coating layer of 10-50nm, converting the asphalt material into graphite at high temperature, reducing the number of groups on the surface of the hard carbon material, obtaining the optimal structural effect of the cathode material, and enabling the prepared hard carbon to have an optimized pore structure.
Compared with the prior art, the slurry has good viscosity, granularity and solid content stability, the prepared membrane has lower resistivity and higher binding power, and the prepared lithium ion battery has good cycle stability and excellent high-low temperature performance, can provide high-power discharge performance, and is suitable for the power battery for the electric automobile with high power density and high energy density.
Detailed Description
The first embodiment is as follows:
(1) placing 500g of coconut shell into a heating pot, placing the heating pot in an atmosphere furnace, introducing N2 under 0.1MPa, enabling the flow rate to be 200sscm, raising the temperature to 550 ℃ after 30 minutes, and enabling the temperature raising speed to be 10C/min. After 2 hours of incubation, coconut shell charcoal was formed.
(2) The prepared coconut shell charcoal was preliminarily pulverized to D50 of 7um using jet milling.
(3) And placing the primarily crushed materials into a material pot, heating to 1350 ℃ under the protection of N2, keeping the temperature at 10 ℃ per min, and preserving the heat for 12 hours to form a hard carbon precursor.
(4) Adding 20g of pitch into a 500mL reactor, raising the temperature to 165 ℃, stirring until the pitch is completely melted, adding 300g of hard carbon precursor, stirring for 2 hours under 165 ℃ to fully mix the hard carbon precursor and the pitch, and cooling to room temperature;
(5) crushing the formed block by using a pair of rollers, and crushing the block to 8um D50 by using air flow; and transferring the crushed particles into a vacuum furnace for coating, heating to 1700 ℃, wherein the vacuum degree is 0.01Pa, and sieving the treated material with a 200-mesh sieve to remove large particles to obtain the hard carbon material used as the negative electrode of the lithium battery.
Example two:
the parameters of the second example are consistent with the parameters of the first example, except that the hard carbon material is prepared without asphalt coating, and the second example comprises the following steps:
(1) placing 500g of coconut shell into a heating pot, placing the heating pot in an atmosphere furnace, introducing N2 under 0.1MPa, enabling the flow rate to be 200sscm, raising the temperature to 550 ℃ after 30 minutes, and enabling the temperature raising speed to be 10C/min. After 2 hours of incubation, coconut shell charcoal was formed.
(2) The prepared coconut shell charcoal was pulverized to D50 of 7um using a gas stream.
(3) And (3) placing the crushed materials into a material bowl, heating to 1150 ℃ under the protection of N2, wherein the heating speed is 10 ℃ per min, and keeping the temperature for 12 hours to form the hard carbon material.
Example three:
example three was consistent with the other process parameters of example one except that the heating temperature in step (3) was 1150 ℃.
Example four:
example four the parameters of the other steps of example one were kept the same, except that 15g of pitch was added in step (4).
Example five:
example five the other process parameters of example one were kept the same except that the heating temperature in step (5) was 2000 ℃.
Example six:
example six the parameters of the other steps of example one were kept the same, except that in step (5) the particle size of D50 was 6 um.
The prepared hard carbon materials in the above embodiments are respectively subjected to electrochemical performance tests, 50g of hard carbon material, 3g of conductive carbon black, 5g of styrene butadiene rubber and 0.5g of carboxymethyl cellulose are dispersed in deionized water, stirred and dispersed to form uniform slurry, and the slurry is transferred to copper foil and dried to form the electrode plate. The pole piece is cut into round electrodes and assembled into a 2032 type button cell in a glove box, the metal lithium piece is used as a counter electrode, and the diaphragm is made of polyethylene. The charging and discharging voltage of the battery is 0-1.5V, and the charging and discharging rate is 0.2C.
The results of the test are shown in table 1:
TABLE 1
As can be seen from the comparison of the remaining examples in table 1 with example two, the pitch-coated hard carbon material is superior in each property to the non-pitch-coated hard carbon material.
The first coulombic efficiency of the hard carbon material without coating asphalt is more than 80 percent, the first discharge capacity is higher than 320mAh/g, and the 500-time cycle life is not less than 75 percent; the first coulombic efficiency of the hard carbon material wrapped with the asphalt is more than 90%, the first discharge capacity is higher than 340mAh/g, the 500-time cycle life is not less than 85%, and the performance of the hard carbon material wrapped with the asphalt is better than that of the hard carbon material not wrapped with the asphalt.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The foregoing is a preferred embodiment of the present invention, and it will be apparent to those skilled in the art that various changes and modifications may be made without departing from the spirit of the invention, and these should be considered to be within the scope of the invention.
Claims (8)
1. A method for preparing a hard carbon material is characterized by comprising the following steps,
s1, pre-carbonizing a carbon-containing raw material with natural components to prepare a precursor;
s2, primarily crushing the precursor to prepare a crushed product;
s3, sintering the crushed material at high temperature in an inert atmosphere for carbonization to obtain a hard carbon precursor;
s4, stirring, heating and mixing the hard carbon precursor and the pitch for coating treatment to obtain a coated product;
and S5, carbonizing the coated hard carbon precursor and the asphalt in vacuum, and crushing and grading to obtain the hard carbon material.
2. A method for preparing a hard carbon material according to claim 1,
in the step S1, the raw material is coconut shell, and the raw material is heated under the protection of N2;
optionally, the heating temperature is 400-700 ℃, and the heating time is 30-120 min.
3. A method for producing a hard carbon material according to claim 2,
in the step S2, the particle size D50 of the material after the primary crushing treatment is 5-50 μm.
4. A method for preparing a hard carbon material according to claim 3,
in S3, the inert atmosphere includes a nitrogen atmosphere, an argon atmosphere, or a helium atmosphere;
preferably, the sintering temperature of carbonization is 1150-1600 ℃, and the treatment time is 1-20 h;
further preferably, the sintering temperature of carbonization is 1350-1425 ℃, and the treatment time is 1-20 h.
5. A method for preparing a hard carbon material according to claim 4,
in S4, the coated hard carbon precursor and pitch are subjected to jet milling,
preferably, the jet milling equipment adopts a jet mill;
preferably, the particle size D50 of the jet milled material is 4-10 μm.
6. A method for producing a hard carbon material according to claim 4 or 5,
in S4, the asphalt coating equipment is a reaction kettle,
preferably, the mass ratio of the pitch to the hard carbon precursor is 1: 13.5-21.5.
7. A method for preparing a hard carbon material according to claim 6,
in S5, heating at 1700-2000 deg.C to convert the pitch into graphite structure;
preferably, the vacuum is less than 0.01 Pa.
8. A method for producing a hard carbon material according to claim 7,
in S5, the average particle diameter of the crushed hard carbon material is 3-25um, the tap density is 0.6-1.2g/cm3, and the specific surface area is 2.5-8.5m 2/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011540987.8A CN112661133A (en) | 2020-12-23 | 2020-12-23 | Preparation method of hard carbon material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011540987.8A CN112661133A (en) | 2020-12-23 | 2020-12-23 | Preparation method of hard carbon material |
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| Publication Number | Publication Date |
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| CN112661133A true CN112661133A (en) | 2021-04-16 |
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| CN202011540987.8A Pending CN112661133A (en) | 2020-12-23 | 2020-12-23 | Preparation method of hard carbon material |
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| CN (1) | CN112661133A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114524425A (en) * | 2022-01-26 | 2022-05-24 | 广东海洋大学 | Hard carbon material, preparation method thereof and application thereof in sodium-ion battery |
| CN115159502A (en) * | 2022-08-18 | 2022-10-11 | 广东邦普循环科技有限公司 | Carbonaceous material, preparation method thereof and sodium ion battery |
| CN115636405A (en) * | 2022-10-31 | 2023-01-24 | 湖州强大分子筛科技有限公司 | Preparation method of high-capacity hard carbon negative electrode material |
| CN117534055A (en) * | 2023-11-29 | 2024-02-09 | 浙江卡波恩新材料有限公司 | Production and manufacturing technology of moso bamboo biomass hard carbon |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101969122A (en) * | 2010-09-14 | 2011-02-09 | 东莞市迈科新能源有限公司 | Core-shell structured carbon for cathode material of lithium ion battery and preparation method thereof |
| CN106185862A (en) * | 2016-06-30 | 2016-12-07 | 中国科学院物理研究所 | A kind of pyrolyzed hard carbon material and application thereof |
-
2020
- 2020-12-23 CN CN202011540987.8A patent/CN112661133A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101969122A (en) * | 2010-09-14 | 2011-02-09 | 东莞市迈科新能源有限公司 | Core-shell structured carbon for cathode material of lithium ion battery and preparation method thereof |
| CN106185862A (en) * | 2016-06-30 | 2016-12-07 | 中国科学院物理研究所 | A kind of pyrolyzed hard carbon material and application thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114524425A (en) * | 2022-01-26 | 2022-05-24 | 广东海洋大学 | Hard carbon material, preparation method thereof and application thereof in sodium-ion battery |
| CN114524425B (en) * | 2022-01-26 | 2024-01-16 | 广东海洋大学 | Hard carbon material, preparation method thereof and application thereof in sodium ion battery |
| CN115159502A (en) * | 2022-08-18 | 2022-10-11 | 广东邦普循环科技有限公司 | Carbonaceous material, preparation method thereof and sodium ion battery |
| WO2024036902A1 (en) * | 2022-08-18 | 2024-02-22 | 广东邦普循环科技有限公司 | Carbonaceous material and preparation method therefor, and sodium-ion battery |
| CN115636405A (en) * | 2022-10-31 | 2023-01-24 | 湖州强大分子筛科技有限公司 | Preparation method of high-capacity hard carbon negative electrode material |
| CN117534055A (en) * | 2023-11-29 | 2024-02-09 | 浙江卡波恩新材料有限公司 | Production and manufacturing technology of moso bamboo biomass hard carbon |
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Application publication date: 20210416 |